Diffusion transfer process employing tone modifiers



United States Patent 3,232,759 DIFFUSIONTRANSFER PROCESS EIVLPLOYINGTONE MODIFIERS- Richard-L; White, Edwin B. Wyand, and Hugh G. McGuckin,Rochester, N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., acorporation of New Jersey N0 Drawing; Filed Sept-13, 1962,Ser. No.223,532 14 Claims. (Cl. 9629)' This invention relates to.the productionof positive photographic images by the methodgenerally known as theditfusiontransfer process, more particularly, a process for improvingthetone of the images obtained thereby.

In the diffusion transfer process alight-sensitive silver halidecontaining emulsion is exposed to lightand a negative image formed in'the photographic emulsion by developing. A silver solvent is used(generally in the developer) to cause diffusion of the unexposed silversalts onto. a receiving sheet held inface contact with the negative. Thereceiving sheet contains development nuclei which cause the diffusedsilver salts to form positive silver or silver salt images 'on thereceiving sheet.

A problem encountered in the diffusion transferprocess has been that ofproducing a neutral positive image since the positive imagewhich'isoften produced is of a brownish or other non-acceptable color.One solution to this-problem has-been disclosed in US. Patent No.3,004,850, issued to Dickinson et al., October 17, 1961.

It has now been found'that a group of compounds can be used eithersingularly or in combination in small amounts and will produce a shiftin the positive image tone toward a neutral color.

One object of this invention is to provide a process for obtaining animproved tone of the positive image obtained in the diffusion transferprocess. Anotherv object is to obtain prints by the diffusion transferprocess having satisfactory colors. Another object is to obtain thesatisfactory neutral color in prints with a shorttransfer time. Anadditional object is to provide a group-- of compounds which can be usedeither singularly or in combination with an amine-type developer forimproving positive image tone.

The above objects are attained by using at least one compound having thegeneral formula:

wherein R1' andR represent identical alkyl groups such as Methyl, Ethyl,Or propyl,

or identical hydroxyalkyl groups such as:

2-hydroxyethyl, Or 2-hydroxy-1-propyl,

or, taken together, represent a saturated ring of five or six atoms suchas:

Morpholinyl, Or piperidyl,

or, if R represents Hydrogen, Or methyl,

R represents hydroxyalkyl groups such as:

Z-hydroxyethyl, LI-dimethy'l-Z-hydroxyethyl,

1,1-(dihydroxymethyl)-ethyl, tris-(hydroxyniethyD-methyl, Or glucosyl;

111 represents a small integer;

n represents an integer between one and" six or a fraction representinga mixture of compounds in which n is between one and six, and

Z represents:

Hydrogen,

Hydrochloride, Cyanamide, as the isothiuronium salt, Formaldehyde, as amercaptal, 7 Or a metal forming a complex, for instance-- Silver, Zinc,Or Zirconium,

with an amine-type developer inthe diffusion transfer process.

isbetween .01 and 10:0 g. per liter in the developingsolution. It willbe clear that the developer containing the tone modifier can be'appliedto the photographic emulsion using the usual means as well' as byincorporating it in a pod and squeezing ;it over the surfaoeof theexposed emulsion. It mayalso be used in conjunction with the webprocessing'method in which the exposed silver halide emulsion"layer'containing' a'latent photocolloid processing element or web. Thisprocessing ele ment contains dispersed silver'precipitat'ing agent, andat least at the'time of contact with'the' exposed emulsion layer,suflicient processing solution to develop the exposed silver-halide andto remove substantially all of the undeveloped silver halide. Forexample, a web'process'ing positive image which comprises exposingaphotographic silver halide emulsion layer to an object or image, developing a negative image in the exposed layer, and during or afterdevelopment, transferring silver halide-by diifusion from the unexposedareas of the emulsion layer to a non-light-sensitive image receivinglayer containing a silver preci itating agent such as development nucleior a substance capable of forming development nuclei with dissolvedsilver halide or a precipitant for silver salts by double decompositionand in effective contact with the emulsion layer, the transfer beingeffected in the presence of a silver halide'solvent and at least onecompound of one of the above general formulas.-

In a preferred embodiment, the silver or zinc salt of the abovecompoundscan be used. For intsance, diethylaminoethaneth-iol HCl can be added tosilver nitrate to form the silver salt and added as the silver salt.

By in effective contact we means that dissolved silver salts can diffusefrom the emulsion layer to the nonlight-sensitive layer. There may beanintermediate'layer present between the two aforesaid layers which doesnot hinder the silver salt diffusion, and the two layers may or may notbe coated on the same support. 7 7

Alkaline solution is used to eifect development of the exposed layer andthe developing agent may be present in either the emulsion layer or inthe alkaline solution or both. A mixture of developing agents may beused, if desired.

The concentration of the above-tone modifier' graphic imageis contactedwith a hydrophilieorg'a'nic The silver halide solvent may be present inthe developing solution or the receiving layer and is preferably sodiumthiosulfate.

It is preferable to employ an antifoggant to prevent the formation offog in the exposed emulsion layer and this may be present in either theemulsion layer or in the alkaline solution used to elfect development.Any of the well known nitrogen-containing organic antifoggants may beused, or inorganic, such as potassium bromide, which are very suitable.

A suitable known light-insensitive image receiving layer for use in thepresent invention comprises a gelatin layer containing a substanceconstituting development nuclei (such as colloidal silver or silversulfide) or a substance forming development nuclei with dissolved silversalts (such as zinc sulfide), and also containing at least one of thecompounds of this inveniton.

Such a layer may be coated on a paper or film support and contacted inthe presence of a silver halide solvent with an exposed and developingemulsion layer which may be coated on a separate support, or may becoated on the same support as the emulsion layer. In the latter, it ispreferable to coat the non-light-sensitive layer on a paper support andthen to overcoat this layer with a comparatively unhardened emulsionlayer. After exposure, development and formation of a direct positiveimage in the nonlight-sensitive layer, the exposed and developedunhardened emulsion layer is removed, for example by washing in warmwater. The following examples are intended to illustrate our inventionbut not to limit it in any way:

Example 1 A coating was made on a white, opaque, cellulose acetatesupport. It was comprised of a 30 mg./ft. nucleated gelatin layer coatedover a 1000 mg/ft. gelatin pad. The nuclei were lead sulfideprecipitated in 1.5% gelatin.

The web coating was soaked for three minutes in a developer consistingof:

Grams 2,2-iminodiethanol-SO addition product, 13% S by weight 200.04,4-dimethyll -phenyl-3 -pyrazolidone l .0 Hydroquinone 1 1.0 Sodiumthiosulfate 8.0 Potassium iodide 0.4 Diet'hylaminoethanethiol HCl 0.053-mercapto-1,2,4-triazole 0.05

Water to make 1 liter.

Example 2 A dry processing web was used which consists of a hydrophiliclayer comprising, in each square foot, 2 g. gelatin, 8 mg. lead sulfidenuclei, a hardener, and a coat- .ing aid coated on polyethyleneterephthalate film support. The dry web was soaked for 3 minutes in adeveloper consisting of:

Grams 2,2-iminodiethanol-SO addition pro duct, 13

S0 by weight 200.0 4-methyl-1-phenyl-3-pyrazolidone 2.0 Hydroquinone 9.0Sodium thiosulfate, crystalline 75.0 Diethylaminoethanethiol HCl 0.5Water to make 1 liter.

Sodium hydroxide to pH 10.00.

The web was removed from the developer and was wound on a spool togetherwith an exposed roll of photographic film having thereon a silver halideemulsion in such a manner that the emulsions of the two strips were incontact. After 10 minutes, the two strips were pulled apart, revealing aneutral tone positive image in the web having a partially fixednegative. After additional fixing, a useable negative obtained, althoughof low contrast. The addition of diethylaminoethanethiol HCl in thisprocess, by itself produce good neutral tones and density in the webimage. Best results were obtained when the negative film was exposed atthe recommended film index of 1250.

Example 3 A processing web was prepared and soaked as in EX- ample 2except that the amount of diethylaminoethanethiol HCl was 0.75 g. perliter, also, the Web-soak time was increased to 5 minutes instead of 3minutes. Two films were exposed at their recommended exposure indexes of80 and 200, respectively, and processed by means of the web. Afteradditional fixing, a useable negative of adequate contrast was obtainedwith both films. The addition of diethylaminoethanethiol I-ICl, as inExample 2, produced good neutral tones and density in the positive webimages.

-Example 4 A processing web was prepared by coating on each square footof a cellulose acetate support, 2 g. gelatin, 8 mg. lead sulfide nuclei,and 9 mg. diethylaminoethanethiol l-ICl, together with a hardener and acoating aid.

The web was soaked for 5 minutes in 5 ccs. of the same developersolution used in Example 2 but with the diethylaminoethanethiol HClomitted. The web was then rolled in contact with an exposed 35mm. rollof highspeed negative gelatino silver bromoiodide photographic filmusing a wind-up type processor. After 10 minutes, the film and web wereseparated.

Neutral tone positive images were obtained in the web after processing.

' Example 5 A receiving sheet was prepared by coating, on each squarefoot of a white pigmented cellulose acetate sup port, 1 g. gelatin, 0.45mg. nickel sulfide nuclei, 260 mg. hypo, 21 mg.5-diethylaminoethyl-iso-thiuronium chloride HCl, and 0.22 mg. 2 mercapto5 phenyl 1,3,4- oxadiazole, together with a hardener and a coating aidThe receiving sheetand a sheet of exposed, very highspeed negativegelatino silver bromoiodide photographic film were both soaked for 15seconds in a developer consisting of:

Grams 2,2iminodiethanol-SO addition product, 13

so by weight 200.0 Hydroquinone 40.0 4-methyl-l-phenyl-3-pyrazolidone0.5

After soaking, the two sheets were brought in contact by means ofwringer rollers. After 1 /2 minutes processing time, the strips werepulled apart to reveal a neutral tone positive image in the receiver.

Example 6 A similar experimental processing web was prepared: as used inExample 4 by coating on a white pigmented cellulose acetate support 1 g.gelatin, 500 mg. hypo, and 10 mg. diethylarninoethanethiol HCl per square foot, to-- gether with a hardener anda coating aid.

The receiver and an exposed sheet of very high-speed.

negative gelatino silver bromoiodide photographic film were each soakedfor 15 seconds in a developer consisting Grams 2,2'-iminodiethanol-SOaddition product, 13%

S0 by weight 100.0

Sodium sulfite .0.

Z-methylhydroquinone 3 0.0 4-methyl-1-phenyl-3-pyrazolidone 0.2Potassium brornide 10.0

Water tomake 1 liter. Sodium hydroxide to pH 11.1.

Processing was carried out as described in ExampleS. Neutral tonesresulted in the positive image of the receiver.

Example 7 A receiver wasipreparedby coatinga layer on 'white pigmentedcellulose acetate support which was comprised of:

Mgjft. Gelatin 360.0- Sodium.sulfite, anhydrous 25.0 Sodiumthio'sulfate, pentahydrate 50.0-

(Ethylenedinitrilo) tetraacetic acid, tetrasodium salt 100.0(Ethylenedinitrilo) tetraacetic acid, trisodiurnsalt- 200.0v Nickelsulfide nuclei 0.18 1..- methyl 1,2,3,6 tetrahydro 1,3,5 triazine-4-thiol 4.0 3,8 dithiadecane 1,10 .bis(-N methylpiperidinium pts.) 10.0

A hardener anda coating, aid were also presentinthecoating solution.Addition-a1 coatings weremade'containing 0.75, 1.5, 3.0,:an d 4.5 mg.diethylaminoethanethiol HCl per square foot. The composition of thenegative may be summarized asfollowsz.

Mg./ft. Support: Cellulose acetate filrnwith antihalation pelloidbacking.

Sheets of the negative materials were exposed, soaked in tap water for 1second, and immediately rolled in contact with the sheets of thereceiver. After 2 minutes, each pair of sheets was separated.

In the absence of diethylaminoethanethiol HCl, a weak, yellowbrown imagewas. formed in the receiver. The addition of the diethylaminoethanethiolHCl to the extent of 1.5 mg. per square foot shifted the tone to neutraland increased the image density considerably. At the level of 4.5 mg.per square foot, the density was slightly higher. However, the levelof3.0 mg. per square foot was preferred for this particular combination.

Example 8 A processing web as described in Example 2 was soaked for 3minutes in a basic processing solution comprising:

Gr m Pe ite Th w t e w ee s and rs lsd in mt st with n eis s st Strip ofi hee e e l t p e i o il r sr i Ph o a i fi mer 5 in te processingperiod, the strips' were separated, The web contained only a faintyellow image.

250 mg. of diethylarninoethanethiol HCl was added per liter ofprocessing solution. A heavy deposit of silver was found in the Webindicating the greater eflioiency of 6: transfer and toning action overthe control. When a similar run was made with the addition of 10 ml. of2- methylarninoethanol per liter, the tone was more'brown than aboveindicating that the toning ,action of the diethylaminoethanethiol HCl ismore efficient in the presence of an amine.

Example 9 A processing web consisting of a cellulose acetate supportcoated,'in each-square f0Ot,With a 500 mg. gelatin layer and a 50 mg.gelatin layer containing 0.18 mg. of nickel sulfide nuclei, both layersmoderately hardened, was soaked for-10 seconds at 90, F. in a processingsolution consisting of Methyladinoethanol-SO addition product, 20% S0 byweight ml 160 Hydroqu-inone g 20 1-phenyl-3-pyrazolidorie g 0.5 Sodiumthiosulfate, pentahydrate g 40 -3dimethylaminopropylisothiuroniumchloride HCl Water to makel liter.

The web was removed from the processing solution,

rolled in contact with a fine-grain silver chlorobromide negativematerial and allowed to process for 30 seconds in a water bath whosetemperature was-"F. The strips were then separated, revealing blue-blackpositive image in the web and a developed negative which required anadditional fixing treatment. The omission of the3-dimethylaminopropylisothiuroniumchloride .HCl from the processingsolution caused theaformation ofan orangecolored positive in the Web.Thefollowing structural,

formula for-3-dirnethylaminopropylisothiuroniumchloride H01:

(3-climethylaminopropylisothluroni um chloride HCl) indicates thereaction which occurs in analkaline solution. The cyanamide groupsplits-off from the isothiuronium salt leaving .the active agent,3-dimethylarnino propanethiol.

Example 10 The processing web of Example 2 was soaked for 3 minutes atroom temperature in a processing solution con-v sisting of;

3-dirnethy-larninopropylisothiuronium chloride HCl 0.5 Wa er to m ke 1r,

The --web-was removed from; the processing solution and rolled incontact with an exposed strip offine-grain. Silver re q id ne t e m t il n. s wha m nner that the two emulsions were in contagt; After 10minutes of't ransfer at room temperature the strips were pulled pa t r el a n a t n p t v i age n the W th and a completely fixed negative,

E mple 11 p o es in s ti nwas p epa e co t n ng a 10wp yt sr f ky m noak n h Z-hyd QXyJA-dimetm ylethylaminooligoethylenesulfidee1,69

Clix HQ 2 NH( 2 2S) 1120B 1,1-dimethyl 2hydroxyethylaminooligoethylenesulfide-1.69 0.75 Water to make 1 liter.

The web of Example 2 was soaked in the solution for 3 minutes, removedand rolled in contact with an exposed strip of a fine-grain silverbromoiodide negative material in such a manner that the two emulsionswere in contact. After ten minutes of transfer at room temperature, thestrips were pulled apart, revealing a blue-black positive image in theweb and a completely fixed negative. When the toning agent was omittedfrom the processing solution, a brown image was formed in the web.

For the oligomeric compounds of the type used in Example 11, higherdegrees of polymerization were also eflective, as in the case of1,l-dimethyl-2-hydroxyethyl aminooligoethylene sulfide-2.9.

C H; HOCH2( 3NH(CH GHzS)z.e

Example 12 An experimental processing web like that of Example 2 wassoaked for ten seconds at 90 F. in a processing solution consisting of:

Methylaminoethanol-SO addition product, 20% S by weight ml 160Hydroquinone grams 20 1-pheny1-3-pyrazolidone do 0.5 Sodium thiosulfate,pentahydrate do 40 l,1-dimethyl-2-hydroxyethylaminooligoethylenesulfide-2.9 grams 0.2

Water to make 1 liter.

The web was removed from the processing solution, rolled in contact withthe negative material of Example 9, and allowed to process for 30seconds in a water bath whose temperature was 90 F. The strips were thenseparated, revealing a blue-black positive image of good density in theweb and a developed negative which required an additional fixingtreatment. Orange tones were obtained in the positive image in the webwhen the toner was omitted from the processing solution.

Example 13 A Web like that of Example 9 was soaked for ten seconds at 90F. in a processing solution consisting of:

Methylaminoethanol ml 50 Sodium sulfite, anhydrous grams 20 Hydroquinonedo 20 4,4-dimethyl-1-phenyl-3-pyrazolidone do 2 Sodium thiosulfate,pentahydrate do 30 Sulfuric acid to pH of 10.0. 1,1 dimet-hyl 2hydroxyethylam-inooligoethylene sulfide-2.9 gr-am 0.5

Water to make 1 liter.

The web was removed from the processing solution, rolled in contact witha moderate-speed silver bromoiodide negative material, and allowed toprocess for 60 seconds in a water bath whose temperature was 90 F. Thestrips were then separated revealing a blue-black positive image in theweb and a developed negative which required an additional fixingtreatment.

A combination of the toner 1,1-dimethyl-2-hydroxyethylaminooligoethylenesulfide 2.9 and diethylaminoethanethiol HCl was found to be particularlyefifective in the photographic system of Example 7.

8 Example 14 The negative of Example 7 was exposed and soaked in tapwater for six seconds. It was then rolled in contact with a receiverwhich was prepared by coating a layer on white-pigmented celluloseacetate support which was comprised of:

Mg./ft. Gelatin 360.0 Sodium sulfite, anhydrous 25.0 Sodium thiosulfate,pentahydrate 50.0

Ethylenediaminetetraacetic acid, tetrasodium salt 100.0Ethylenediaminetetraacetic acid,trisodium salt 200.01

Nickel sulfide nuclei 0.14 Diethylaminoethanethiol HCl 19.2; Sulfuricacid to pH of 10.0. l,l-dimethyl-2-hydroxyethylaminooligoethylene sultide-2.9 "gram" 0.5

together with a hardener and a coating aid. After two minutes, the twosheets were separated. The receiver contained a high-density,neutral-toned positive image.

Other compounds similar to2-hyd-roxy-1,1-dimethylethylaminooligoethylenesulfide-1.69 and1,1-dimethyl-2- hydroxyethylaminooligoethylenesulfide-2.9 were found tobe effective in combination with diethylaminoethanethiol HCl in thesystem of Example 14.

2-hydroxyethylaminooligoethylene sulfide-1N-methylglucaminooligoethylene sulfide-5 .6

5 HO oH2(ononnommomcmsmrt N(Z-aminoethyl)-2-hydroxyethylaminooligoethylene sulfide-1.75

CH GHZ V ornonzs qfin HzNCHzCHz Morpholinoethanethiol v (\S EW-CHzCHzSH2 morpholinoethylisothiuronium, chloride hydrochloride (ll-.HCl

Example 15 Strips of a negative like that described in Example 7 wereexposed, soaked for six seconds in water or a solution comprising 0.75gram of diethylaminoethanethio] HCl per liter, and then placed incontact with a receiver 9 like that of Example 14 except that the tonerswere omitted. The receiver images had the following appearance:

Solution Transfer time Receiver image appearance Water 2 min Orange.Diethylnminoethane- 2 min Weak brown.

thiol H01.

D 3 min Neutral, high density.

Example -1 6 A negative whose composition may be summarizedas follows:Support: Cellulose acetate film with antihalation pelloid .was exposedand soaked ,for six seconds in a solution containing approximately 500.mg. diethylarninoethanethiol .and 200 mg.1,1edimethyl-Lhydroxymethy-laminooligeethylene sulfide-2.9 perliter.Both compoundswerepresent in the solution as silver complex salts,formed by combining one mole of silver nitrate with two moles of theorganic compound. The formation of a tightlybound complex was indicatedby the disappearance ofthe characteristic odor of each compound. Aftersoaking, the negative was rolled in contact with a receiver like that ofExample 14 but from which the toners had been omitted. After threeminutes, the two sheets were separated, revealing a neutral-tonedpositive image in the receiver.

Example I 7 The experiment of the preceding example was repeated withthe water for soaking the negative containing 0.5 gram of2-dimethylaminoethylmercapto zinc chloride hydrochloride and 2.0 gramsof 2-morpholinoethylisothiuronium chloride hydrochloride per liter. Aneutral-toned positive image was obtained.

Example 18 Processing web A was prepared which comprised, per squarefoot, 2000 mg. gelatin, nickel sulfide nuclei, 12 mg.diethylaminoethanethiol, a hardener and a coating aid, coated on apolyethylene terephthalate support. In a second web, B, the 12 mg. ofdiethylaminoethanethiol had previously been combined with 6 mg. ofsilver nitrate. The webs were soaked for periods of time ranging from 11 to 12 minutes at 70 F. in a processing solution comprising:

Grams 2,2'-iminodiethanOl-SO addition product, 12.8%

S0 by weight 200 4,4-dimethyl-1-phenyl-3-pyrazolidone 2 HydroquinoneSodium thiosulfate, pentahydrate 100 Sodium hydroxide to pH 10.5. Waterto make 1 liter.

and placed in contact with exposed strips of a fine-grain gelatinosilver bromoiodide negative for ten minutes.

The negatives for both webs showed only a slight increase in speed andcontrast as the web soak time was in creased. The positive images in WebA showed a progressive lowering of contrast, as represented by alengthening of the toe and a falling off of the shoulder, as the soaktime was increased. The shape and position of the positive curve in WebB was not influenced by the length of 10 the soak period. It was evidentthat the diethylaminoethanethiol was slowly washed out of Web A duringthe soaking period, while, as the silver salt in Web B, the loss of thecompound was eliminated or at least greatly reduced.

Example 19 Processing webs like those of Example 18 above were preparedin which Web C contained no toning agent and Web D contained 4 mg. ofdiethylaminoethanethiol per square footcomplexed with 2 mg. of silvernitrate. Samples of the two webs were incubated for one week at 100 F.and percent relative humidity. The incubated and non-incubated Webs weresoaked for 4 minutes at 70 F. in a solutioncomprised of:

Grams Methylaminoethanol-SO addition product, 19% S0 by weight Dimezone2 Hydroquinone 10 Sodium thiosulfate, pentahydrate 100 Ethanol 100 Waterto make 1 liter.

and placed in contact withexposed strips of a fine-grain gelatino silverbromoiodide negative material for ten minutes. Incubation of theprocessing webs caused the positive image curves ,to be shifted inadirectionrepresent- Processing Web A is prepared. as described inExample 18 except that in the second web, B, the 12 mg. ofdiethylaminoethanethiol is combined with 6 mg. of Zinc nitrate. Theweb-s are soaked for periods of time ranging from 1 to 12 minutes at 70F. in the processing solutiondescribed in Example 18, and placed incontact with exposed strips of a fine-grain gelatino silver brornoiodidenegative for ten minutes.

The negatives for both webs show only a slight increase in speed andcontrast as the web soak time was increased. The positive images in WebA show a progressive lowering of contrast as represented by alengthening .of the toe and a falling off of the shoulder, as the soaktime is increased. The shape and position ofthe ositive curve in Web Bis not influenced by the length of the soak period. It is evident thatthe diethylaminoethanethiol is slowly washed out of Web A during thesoaking period, while, as the Zinc salt in Web B, the loss of thecompound is eliminated or least greatly reduced.

Example 21 aminoethanet-hio-l the same amount of transfer can take placein 15 or 20 seconds. The effect was observed a. diffusion transfersystem containing a toning agent com: bination disclosed and claimed inthe Tregillus et al. US. Patent No. 3,017,270 as extended by the US,patent ap= plication Ser. No. 141,036, filed September 27, 1961 and nowabandoned, by A. A. Rasch, P. B. Gilman, and J. E. Jones.

A fine-grain gelatino silver bromoiodide negative film was exposed andthen dipped for six seconds at 70 F. in a solution comprising:

Grams 2,2'-iminodiethanol-SO addition product, 12.8%

80 by weight 160.0 Methylaminoethanol-SO addition product, 19%

S by weight 20.0 1-phenyl-3-pyrazolidone 1.0 Hydroquinone 12.0 Sodiumthiosulfate, pentahydrate 60.0 Triton X-200 (surfactant) 0.5 Sodiumhydroxide to pH 10.5.

Water to make 1 liter.

As Run A, the negative was immediately placed in contact for 20 secondsat 70 F. with a receiver consisting of a white-pigmented at 70 F. with areceiver consisting of coated, per sq. ft., 1000 mg. gelatin, 0.3 mg.nickel sulfide nuclei, a hardener, and a coating aid.

Run A was repeated with the following changes:

Run B.2.0 grams per liter of 3.8-dithiadecane-Ll0-bis(N-methylpiperidiniurn-p-toluene sulfonate) were added to theprocessing solution.

Run C.0.1 gram of l-methyl-1,2,3,6-tetrahydro- 1,3,5-triazine-4-thiolwere added to one liter of the processing solution.

Run D.The additions of Runs B and C were combined.

Run E.The negative was dipped in the solution of Run D and placed incontact with a receiver containing, in addition, a complex formed bycombining 4 mg. of diethylaminoethanethiol and 2 mg. of silver nitrate.

The positive images in the receivers of the various runs were found topossess the following characteristics:

Subsequently, the receiver and processing solution were modifiedslightly and rebalanced so that the image tone was substantially neutraland the maximum density was on the order of 1.6.

Polymeric sulfides described as useful in this invention are describedin pending US. patent application 165,931, filed January 12, 1962 andnow abandoned, in the names of Johnson and Reynolds.

The invention has been described in detail wth particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention as described hereinabove and as defined in the appendedclaims.

We claim:

1. A process for preparing a photographic image which comprisesdeveloping an exposed photographic silver halide emulsion layer with asilver halide developing agent and transferring the silver halide bydiffusion from the undeveloped areas of the emulsion layer to asupported image receiving layer containing developing nuclei, transferbeing effected in contiguity with sufficient silver halide solvent toremove substantially all undeveloped silver halide from the emulsionlayer, an alkanolamine and, in addition, a toning compound, saidcompound being different from the silver halide solvent, having thegeneral formula:

wherein R and R are selected from the class consisting from the classconsisting of hydrogen, iminocarbamoyl,

hydroxymethyl, silver, zinc and Zirconium.

2. The process of claim 1 wherein the toning compound is incorporated inthe developer solution.

3. The process of claim 1 wherein the toning compound is incorporated inthe image receiving layer.

4. A process for preparing a photographic image which comprisesdeveloping an exposed photographic sil ver halide emulsion layer with asilver halide developing agent and transferring the silver halide bydiffusion from the undeveloped areas of the emulsion layer to asupported image receiving layer containing development nuclei, thetransfer being effected in contiguity with sufficient silver halidesolvent, other than diethylatninoethanethiol HCl, to removesubstantially all undeveloped silver halide from the emulsion layer, analkanolamine and, in addition, diethylaminoethanethiol HCl.

5. A process for preparing a photographic image which comprisesdeveloping an exposed photographic silver halide emulsion layer with asilver halide developing agent and transferring the silver halide bydilfusion from the undeveloped areas of the emulsion layer to asupported image receiving layer containing development nuclei, thetransfer being effected in contiguity with sufiicient silver halidesolvent to remove substantially all undeveloped silver halide from theemulsion layer, an alkanolamine and, in addition,2-hydroxyethylaminooligoethylene sulfide.

6. A process for preparing a photographic image which comprisesdeveloping an exposed photographic silver halide emulsion layer with asilver halide developing agent and transferring the silver halide bydiffusion from the undeveloped areas of the emulsion layer to asupported image receiving layer containing development nuclei, thetransfer being effected in contiguity with sufficient silver halidesolvent to remove substantially all undeveloped silver halide from theemulsion layer, an alkanolamine and, in addition,2-hydroxy-1,1-dimethylethylaminooligoethylene sulfide.

7. A process for preparing a photographic image which comprisesdeveloping an exposed photographic silver halide emulsion layer with asilver halide developing agent and transferring the silver halide bydiffusion from the undeveloped areas of the emulsion layer to asupported image receiving layer containing development nuclei, thetransfer being effected in contiguity with sulficient silver halidesolvent to remove substantially all undeveloped silver halide from theemulsion layer, an alkanolamine and, in addition, morpholinoethanethiol.

8. A process for preparing a photographic image which comprisesdeveloping an exposed photographic silver halide emulsion layer with asilver halide developing agent and transferring the silver halide bydiffusion from the undeveloped areas of the emulsion layer to asupported image receiving layer containing development nuclei, thetransfer being effected in contiguity with sufficient silver halidesolvent to remove substantially all undeveloped silver halide from theemulsion layer, an alkanolamine and, in addition, 1-1-(dihydroxymethyl)-ethylaminooligoethylene sulfide.

9. A process for preparing a photographic image which comprisesdeveloping an exposed photographic silver halide emulsion layer with asilver halide developing agent and transferring the silver halide bydiffusion from the undeveloped areas of the emulsion layer to asupported image receiving layer containing development nuclei, thetransfer being effected in contiguity with Sllfil cient silver halidesolvent to remove substantially all undeveloped silver halide from theemulsion layer, an

alkanolamine and, in addition,tris-hydroxymethylmethylaminooligoethylene sulfide.

10. A process for preparing a photographic image which comprisesdeveloping an exposed photographic silver halide emulsion layer with asilver halide developing agent and transferring the silver halide bydiffusion from the undeveloped areas of the emulsion layer to asupported image receiving layer containing development nuclei, thetransfer being effected in contiguity with sufiicient silver halidesolvent to remove substantially all un developed silver halide from theemulsion layer, an alkanolarnine and, in addition,bis(2-hydroxy-l-propyl) aminooligoethylene sulfide.

11. A process for preparing a photographic image which comprisesdeveloping an exposed photographic silver halide emulsion layer with asilver halide developing agent and transferring the silver halide bydiffusion from the undeveloped areas of the emulsion layer to asupported image receiving layer containing development nuclei, thetransfer being effected in contiguity With sufllcient silver halidesolvent to remove substantially all undeveloped silver halide from theemulsion layer, an alkanolamine and, in addition,N-methylglucaminooligoethylene sulfide.

12. A process for preparing a photographic image which comprisesdeveloping an exposed photographic silver halide emulsion layer with asilver halide developing agent and transferring the silver halide bydiffusion from the undeveloped areas of the emulsion layer to asupported image receiving layer containing development nuclei, thetransfer being effected in contiguity with sufficient silver halidesolvent to remove substantially all undeveloped silver halide from theemulsion layer, an alkanolamine and, in addition, N-(2-aminoethyl)-2-hydroxyethylaminooligoethylene sulfide.

13. A process for preparing a photographic image which comprisesdeveloping an exposed photographic silver halide emulsion layer With asilver halide developing agent and transferring the silver halide bydiffusion from the undeveloped areas of the emulsion layer to asupported image receiving layer containing development nuclei, thetransfer being effected in contiguity with sufficient silver halidesolvent to remove substantially all undeveloped silver halide from theemulsion layer, an alk-anolamine and, in addition, the silver salt ofdiethylaminoethanethiol HCl.

14. A process for preparing a photographic image which comprisesdeveloping an exposed photographic silver halide emulsion layer with asilver halide developing agent and transferring the silver halide bydiffusion from the undeveloped areas of the emulsion layer to asupported image receiving layer containing development nuclei, thetransfer being effected in contiguity with sufficient silver halidesolvent to remove substantially all undeveloped silver halide from theemulsion layer, an alkanolamine and, in addition, the zinc salt ofdiethylaminoethanethiol HCl.

References Cited by the Examiner UNITED STATES PATENTS 2,698,245 12/1954Land 96-29 2,875,048 2/1959 Haist et al. 96-61 2,984,565 5/1961 Morse96-29 3,017,270 1/1962 Tregillus 96--29 FOREIGN PATENTS 594,237 Belgium.1,243,430 9/1960 France.

OTHER REFERENCES Photographic Science and Engineering, 5, July-August1961, pp. 198-203.

NORMAN G. TORCHIN, Primary Examiner.

1. A PROCESS FOR PREPARING A PHOTOGRAPHIC IMAGE WHICH COMPRISESDEVELOPING AN EXPOSED PHOTOGRAPHIC SILVER HALIDE EMULSION LAYER WITH ASILVER HALIDE DEVELOPING AGENT AND TRANSFERRING THE SILVER HALIDE BYDIFFUSION FROM THE UNDEVELOPED AREAS OF THE EMULSION LAYER TO ASUPPORTED IMAGE RECEIVING LAYER CONTAININ DEELOPING NUCLEI, TRANSFERBEING EFFECTED IN CONTIGUITY WITH SUFFICIENT SILVER HALIDE SOLVENT TOREMOVE SUBSTANTIALLY ALL UNDEVELOPED SILVER HALIDE FROM THE EMULSIONLAYER, AN ALKANOLAMINE AND IN ADDITION, A TONING COMPOUND, SAID COMPOUNDBEING DIFFERENT FROM THE SILVER HALIDE SOLVENT, HAVING THE GENERALFORMULA: